JP2017004732A - Conductive paste - Google Patents
Conductive paste Download PDFInfo
- Publication number
- JP2017004732A JP2017004732A JP2015116858A JP2015116858A JP2017004732A JP 2017004732 A JP2017004732 A JP 2017004732A JP 2015116858 A JP2015116858 A JP 2015116858A JP 2015116858 A JP2015116858 A JP 2015116858A JP 2017004732 A JP2017004732 A JP 2017004732A
- Authority
- JP
- Japan
- Prior art keywords
- weight
- parts
- conductive paste
- copper powder
- phenoxy resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 77
- 229910052709 silver Inorganic materials 0.000 claims abstract description 76
- 239000004332 silver Substances 0.000 claims abstract description 76
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 65
- 239000013034 phenoxy resin Substances 0.000 claims abstract description 45
- 229920006287 phenoxy resin Polymers 0.000 claims abstract description 45
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims abstract description 34
- 150000001875 compounds Chemical class 0.000 claims abstract description 34
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims abstract description 34
- -1 isocyanate compound Chemical class 0.000 claims abstract description 32
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 32
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 32
- 239000012948 isocyanate Substances 0.000 claims abstract description 27
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 24
- 239000011574 phosphorus Substances 0.000 claims abstract description 24
- 239000002245 particle Substances 0.000 claims description 29
- 229910052802 copper Inorganic materials 0.000 claims description 13
- 239000010949 copper Substances 0.000 claims description 13
- 150000001879 copper Chemical class 0.000 claims 1
- 150000003378 silver Chemical class 0.000 claims 1
- 238000005476 soldering Methods 0.000 abstract description 4
- 229910000679 solder Inorganic materials 0.000 description 31
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 22
- 239000010410 layer Substances 0.000 description 20
- 238000000576 coating method Methods 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 14
- 239000011248 coating agent Substances 0.000 description 13
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 12
- UMHKOAYRTRADAT-UHFFFAOYSA-N [hydroxy(octoxy)phosphoryl] octyl hydrogen phosphate Chemical compound CCCCCCCCOP(O)(=O)OP(O)(=O)OCCCCCCCC UMHKOAYRTRADAT-UHFFFAOYSA-N 0.000 description 12
- 238000000034 method Methods 0.000 description 12
- 239000002966 varnish Substances 0.000 description 12
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 10
- 239000002518 antifoaming agent Substances 0.000 description 9
- 239000011230 binding agent Substances 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 239000000758 substrate Substances 0.000 description 8
- 238000002156 mixing Methods 0.000 description 7
- 238000007650 screen-printing Methods 0.000 description 7
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- 238000001723 curing Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 238000007639 printing Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000009736 wetting Methods 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 239000002981 blocking agent Substances 0.000 description 3
- 239000011247 coating layer Substances 0.000 description 3
- 239000004020 conductor Substances 0.000 description 3
- 238000013007 heat curing Methods 0.000 description 3
- 239000005011 phenolic resin Substances 0.000 description 3
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- 229930185605 Bisphenol Natural products 0.000 description 2
- 229920002799 BoPET Polymers 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- IDCBOTIENDVCBQ-UHFFFAOYSA-N TEPP Chemical compound CCOP(=O)(OCC)OP(=O)(OCC)OCC IDCBOTIENDVCBQ-UHFFFAOYSA-N 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical class SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- XMQYIPNJVLNWOE-UHFFFAOYSA-N dioctyl hydrogen phosphite Chemical compound CCCCCCCCOP(O)OCCCCCCCC XMQYIPNJVLNWOE-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- VTIXMGZYGRZMAW-UHFFFAOYSA-N ditridecyl hydrogen phosphite Chemical compound CCCCCCCCCCCCCOP(O)OCCCCCCCCCCCCC VTIXMGZYGRZMAW-UHFFFAOYSA-N 0.000 description 1
- XHWQYYPUYFYELO-UHFFFAOYSA-N ditridecyl phosphite Chemical compound CCCCCCCCCCCCCOP([O-])OCCCCCCCCCCCCC XHWQYYPUYFYELO-UHFFFAOYSA-N 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 238000007646 gravure printing Methods 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- RHZWSUVWRRXEJF-UHFFFAOYSA-N indium tin Chemical compound [In].[Sn] RHZWSUVWRRXEJF-UHFFFAOYSA-N 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 150000003217 pyrazoles Chemical class 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000000790 scattering method Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/52—Electrically conductive inks
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/16—Catalysts
- C08G18/22—Catalysts containing metal compounds
- C08G18/222—Catalysts containing metal compounds metal compounds not provided for in groups C08G18/225 - C08G18/26
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3271—Hydroxyamines
- C08G18/3278—Hydroxyamines containing at least three hydroxy groups
- C08G18/3281—Hydroxyamines containing at least three hydroxy groups containing three hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/58—Epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/6505—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen the low-molecular compounds being compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6523—Compounds of group C08G18/3225 or C08G18/3271 or polyamines of C08G18/38
- C08G18/6535—Compounds of group C08G18/3271
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
- C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
- C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/80—Masked polyisocyanates
- C08G18/8061—Masked polyisocyanates masked with compounds having only one group containing active hydrogen
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
- C09D11/037—Printing inks characterised by features other than the chemical nature of the binder characterised by the pigment
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/24—Electrically-conducting paints
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
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- C09D7/40—Additives
- C09D7/66—Additives characterised by particle size
- C09D7/69—Particle size larger than 1000 nm
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
- C08K2003/0806—Silver
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
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Abstract
Description
本発明は、導電性ペーストに関する。 The present invention relates to a conductive paste.
近年、携帯電話に代表されるモバイル機器には、例えばタッチセンサーの電極として、透明導電性フィルムが用いられている。この透明導電性フィルムとしては、PETフィルム等の透明樹脂フィルム(基材)上に、ITO(インジウム・スズ複合酸化物)等の金属酸化物から構成される透明導電層を形成して得られる透明導電性フィルムが多用されている。ITOから構成される透明導電層は、基材上に、蒸着またはスパッタリングによりITOコーティング層を形成した後、該コーティング層をエッチングすることにより回路形成して、得られ得る。 In recent years, a transparent conductive film is used as an electrode of, for example, a touch sensor in a mobile device typified by a mobile phone. As this transparent conductive film, a transparent conductive layer obtained by forming a transparent conductive layer composed of a metal oxide such as ITO (indium-tin composite oxide) on a transparent resin film (base material) such as a PET film. Conductive films are frequently used. A transparent conductive layer composed of ITO can be obtained by forming a circuit on a substrate by forming an ITO coating layer by vapor deposition or sputtering and then etching the coating layer.
通常、透明導電層上には、種々の部品が実装される。ITOから構成される透明導電層上には、はんだにより部品を実装することができないため、導電性接着剤を用いて部品を固着するという方法が用いられている。また、透明導電層におけるITO回路の周辺に銀ペーストによる回路を配し、銀ペースト回路上に導電性接着剤を介して部品を固着する、あるいは、はんだにより銀ペースト上に部品を実装する等の方法が用いられることもある。 Usually, various components are mounted on the transparent conductive layer. Since a component cannot be mounted on the transparent conductive layer made of ITO by solder, a method of fixing the component using a conductive adhesive is used. In addition, a circuit made of silver paste is arranged around the ITO circuit in the transparent conductive layer, and the component is fixed on the silver paste circuit via a conductive adhesive, or the component is mounted on the silver paste with solder. A method may be used.
しかしながら、導電性接着剤を用いた場合、部品のリペアが困難であるという問題がある。また、銀ペースト上にはんだで部品を実装する場合、はんだに銀が取り込まれて銀ペースト部分が消失するという現象(いわゆる、銀喰われ)が生じやすく、このような現象を抑制するためには、多量の銀を含むはんだを用いることが必要となる。したがって、銀ペーストを用いる上記方法においては、銀ペーストが高価であることに加えて、高価なはんだを用いることとなり、コストが高くなるという問題がある。 However, when a conductive adhesive is used, there is a problem that it is difficult to repair parts. Also, when mounting parts with solder on the silver paste, a phenomenon (so-called silver erosion) in which silver is taken into the solder and the silver paste part disappears easily occurs. It is necessary to use a solder containing a large amount of silver. Therefore, in the above method using the silver paste, in addition to the silver paste being expensive, there is a problem that an expensive solder is used and the cost is increased.
上記問題を解消するため、銀粉よりも安価な銀コート銅粉と、フェノール樹脂とを組み合わせた導電性ペーストが提案されている(特許文献1)。しかしながら、該導電性ペーストは、硬化温度が高い(例えば、140℃以上)という問題がある。このような導電性ペーストを、透明導電性フィルム上に塗工する場合、加熱硬化時に透明導電性フィルムの基材が収縮する場合が多い。また、フェノール樹脂から構成される導電性ペーストは、ITO層との密着性が不十分であるという問題もある。 In order to solve the above problem, a conductive paste in which a silver-coated copper powder that is cheaper than silver powder and a phenol resin is combined has been proposed (Patent Document 1). However, the conductive paste has a problem that the curing temperature is high (for example, 140 ° C. or higher). When such a conductive paste is applied on a transparent conductive film, the substrate of the transparent conductive film often shrinks during heat curing. Moreover, the conductive paste comprised from a phenol resin also has the problem that adhesiveness with an ITO layer is inadequate.
本発明は上記従来の課題を解決するためになされたものであり、その目的とするところは、はんだ付けが可能な導電性ペーストであって、低温で硬化し、ITO層との密着性に優れ、かつ、安価な導電性ペーストを提供することにある。 The present invention has been made in order to solve the above-described conventional problems. The object of the present invention is a conductive paste that can be soldered, cured at a low temperature, and excellent in adhesion to the ITO layer. Another object of the present invention is to provide an inexpensive conductive paste.
本発明の導電性ペーストは、フレーク状銀コート銅粉と、フェノキシ樹脂と、ヘキサメチレンジイソシアネート系ポリイソシアネート化合物および/またはブロックイソシアネート化合物と、リン含有有機チタネートと、アルカノールアミンとを含み、該フレーク状銀コート銅粉の含有割合が、該フレーク状銀コート銅粉と、前記フェノキシ樹脂と、前記ヘキサメチレンジイソシアネート系ポリイソシアネート化合物およびブロックイソシアネート化合物との合計量100重量部に対して、88重量部〜92重量部である。
1つの実施形態においては、上記フレーク状銀コート銅粉の平均粒子径が、5μm〜25μmである。
1つの実施形態においては、上記フレーク状銀コート銅粉が、核となる銅粒子と、該銅粒子をコートする銀コートとから構成され、該銀コートの重量割合が、該銅粒子に対して、5重量%〜20重量%である。
1つの実施形態においては、上記フェノキシ樹脂の含有割合が、該フェノキシ樹脂と前記ヘキサメチレンジイソシアネート系ポリイソシアネート化合物およびブロックイソシアネート化合物との合計量100重量部に対して、40重量部〜65重量部である。
1つの実施形態においては、上記リン含有有機チタネートの含有割合が、前記フレーク状銀コート銅粉100重量部に対して、1重量部〜3重量部である。
1つの実施形態においては、上記アルカノールアミンの含有割合が、前記フレーク状銀コート銅粉100重量部に対して、1重量部〜3重量部である。
The conductive paste of the present invention comprises flaky silver-coated copper powder, a phenoxy resin, a hexamethylene diisocyanate polyisocyanate compound and / or a blocked isocyanate compound, a phosphorus-containing organic titanate, and an alkanolamine. The content ratio of the silver-coated copper powder is 88 parts by weight to 100 parts by weight of the total amount of the flaky silver-coated copper powder, the phenoxy resin, the hexamethylene diisocyanate polyisocyanate compound, and the blocked isocyanate compound. 92 parts by weight.
In one embodiment, the average particle diameter of the said flaky silver coat copper powder is 5 micrometers-25 micrometers.
In one embodiment, the flaky silver-coated copper powder is composed of core copper particles and a silver coat that coats the copper particles, and the weight ratio of the silver coat is based on the copper particles. 5% by weight to 20% by weight.
In one embodiment, the content ratio of the phenoxy resin is 40 parts by weight to 65 parts by weight with respect to 100 parts by weight of the total amount of the phenoxy resin, the hexamethylene diisocyanate polyisocyanate compound, and the blocked isocyanate compound. is there.
In one embodiment, the content rate of the said phosphorus containing organic titanate is 1 weight part-3 weight part with respect to 100 weight part of the said flaky silver coat copper powder.
In one embodiment, the content rate of the said alkanolamine is 1 weight part-3 weight part with respect to 100 weight part of said flaky silver coat copper powder.
本発明によれば、導電性材料として特定量のフレーク状銀コート銅粉を用い、バインダー成分としてフェノキシ樹脂を用い、さらに、ヘキサメチレンジイソシアネート系ポリイソシアネート化合物および/またはブロックイソシアネート化合物と、リン含有有機チタネートと、アルカノールアミンとを添加することにより、低温で硬化し、はんだ付け性およびITO層との密着性に優れ、かつ、安価な導電性ペーストを得ることができる。 According to the present invention, a specific amount of flaky silver-coated copper powder is used as a conductive material, a phenoxy resin is used as a binder component, a hexamethylene diisocyanate-based polyisocyanate compound and / or a blocked isocyanate compound, and a phosphorus-containing organic material By adding titanate and alkanolamine, it is possible to obtain a conductive paste that cures at a low temperature, has excellent solderability and adhesion to the ITO layer, and is inexpensive.
A.導電性ペーストの概要
本発明の導電性ペーストは、フレーク状銀コート銅粉と、フェノキシ樹脂と、ヘキサメチレンジイソシアネート系ポリイソシアネート化合物および/またはブロックイソシアネート化合物と、リン含有有機チタネートと、アルカノールアミンとを含む。本発明の導電性ペーストは、任意の適切なフィルム(例えば、透明導電性フィルム)に塗布し、その後、硬化させて用いられ得る。硬化後の導電性ペーストは、はんだ濡れ性に優れるため、該導電性ペーストを用いれば、はんだ付けによる部品実装が可能となる。また、本発明の導電性ペーストは、ITOとの密着性に優れ、例えば、透明導電性フィルムに形成されたITO層上に塗工する導電性ペーストとして好適に用いられ得る。
A. Outline of Conductive Paste The conductive paste of the present invention comprises flaky silver-coated copper powder, phenoxy resin, hexamethylene diisocyanate polyisocyanate compound and / or blocked isocyanate compound, phosphorus-containing organic titanate, and alkanolamine. Including. The conductive paste of the present invention can be used after being applied to any appropriate film (for example, a transparent conductive film) and then cured. Since the conductive paste after curing is excellent in solder wettability, if the conductive paste is used, component mounting by soldering becomes possible. In addition, the conductive paste of the present invention is excellent in adhesion with ITO, and can be suitably used, for example, as a conductive paste applied on an ITO layer formed on a transparent conductive film.
上記フレーク状銀コート銅粉は、導電性材料として機能する。本発明においては、フレーク状銀コート銅粉の含有量を特定の量とすることにより、はんだに対する濡れ性に優れる導電性ペーストを得ることができる。詳細は後述する。 The flaky silver-coated copper powder functions as a conductive material. In this invention, the electroconductive paste which is excellent in the wettability with respect to a solder can be obtained by making content of flaky silver coat copper powder into a specific quantity. Details will be described later.
また、フェノキシ樹脂、ヘキサメチレンジイソシアネート系ポリイソシアネート化合物およびブロックイソシアネート化合物は、硬化処理により架橋体を形成し、該架橋体がバインダーとして機能する。本発明においては、バインダー成分として、フェノキシ樹脂と、ヘキサメチレンジイソシアネート系ポリイソシアネート化合物および/またはブロックイソシアネート化合物とを用いることにより、ITO層との密着性に優れ、かつ、はんだによる喰われを防止し得る導電性ペーストを得ることができる。また、上記バインダー成分を用いることにより、低温(例えば、130℃以下)で硬化し得る導電性ペーストを得ることができる。このような導電性ペーストを用いれば、透明導電性フィルム上で該ペーストを硬化させる際、該透明導電性フィルムの熱収縮が抑制される。このような効果を発揮する本発明の導電性ペーストは、耐熱性の低い基材(例えば、PETフィルム基材)を含む透明導電性フィルムに対して、好適に用いられる。 Moreover, a phenoxy resin, a hexamethylene diisocyanate polyisocyanate compound, and a block isocyanate compound form a crosslinked body by a curing treatment, and the crosslinked body functions as a binder. In the present invention, by using a phenoxy resin, a hexamethylene diisocyanate polyisocyanate compound and / or a blocked isocyanate compound as a binder component, it has excellent adhesion to the ITO layer and prevents biting by solder. A conductive paste can be obtained. Moreover, the conductive paste which can be hardened | cured at low temperature (for example, 130 degrees C or less) can be obtained by using the said binder component. When such a conductive paste is used, when the paste is cured on the transparent conductive film, thermal shrinkage of the transparent conductive film is suppressed. The conductive paste of the present invention that exhibits such an effect is suitably used for a transparent conductive film including a substrate having low heat resistance (for example, a PET film substrate).
さらに、上記リン含有有機チタネートを添加することにより、上記フレーク状銀コート銅粉の分散性、およびはんだに対する濡れ性に優れる導電性ペーストを得ることができる。また、リン含有有機チタネートを添加することにより、ITO層との密着性が向上する。 Furthermore, the conductive paste excellent in the dispersibility of the said flaky silver coat copper powder and the wettability with respect to a solder can be obtained by adding the said phosphorus containing organic titanate. Moreover, adhesiveness with an ITO layer improves by adding phosphorus containing organic titanate.
上記バインダー成分と、リン含有有機チタネートとを組み合わせて得られた導電性ペーストは、はんだを透過させにくい特性を有する。このような導電性ペーストを用いれば、はんだ付け時、はんだが導電性ペースト裏面(ITO層と接触する面)にまで到達し難く、導電性ペーストとITO層との密着性が維持される。すなわち、本発明の導電性ペーストは、ITO層に対して適切な親和性を示すとともに、はんだを透過させにくいという特性を有するため、ITO層との密着性が非常に高い。 The conductive paste obtained by combining the binder component and the phosphorus-containing organic titanate has characteristics that make it difficult for solder to pass therethrough. When such a conductive paste is used, it is difficult for the solder to reach the back surface of the conductive paste (the surface in contact with the ITO layer) during soldering, and the adhesion between the conductive paste and the ITO layer is maintained. In other words, the conductive paste of the present invention has an appropriate affinity for the ITO layer and has a characteristic that the solder is difficult to permeate, and therefore has very high adhesion to the ITO layer.
B.フレーク状銀コート銅粉
上記フレーク状銀コート銅粉は、核となる銅粒子と、該銅粒子をコートする銀コートとから構成される。銀コートは、銅粒子表面の一部をコートしていてもよく、銅粒子表面の全体をコートしていてもよい。好ましくは、銀コートは、銅粒子表面の全体をコートする。フレーク状銀コート銅粉を用いれば、はんだに対する濡れ性に優れ、はんだによる喰われが防止され得る導電性ペーストを安価に得ることができる。また、フレーク状の銀コート銅粉は、上記バインダー成分中での分散性に優れる点で有利である。
B. Flaky silver-coated copper powder The flaky silver-coated copper powder is composed of core copper particles and a silver coat that coats the copper particles. The silver coat may coat a part of the copper particle surface, or may coat the entire copper particle surface. Preferably, the silver coat coats the entire copper particle surface. If the flaky silver-coated copper powder is used, a conductive paste that is excellent in wettability with respect to solder and that can be prevented from being eaten by solder can be obtained at low cost. Further, the flaky silver-coated copper powder is advantageous in that it is excellent in dispersibility in the binder component.
本明細書において、フレーク状とは、平板または厚みの薄い直方体に近い形状を意味し、具体的には、アスペクト比(長軸長さL/厚みt)が3以上の形状を意味する。該アスペクト比の上限は、例えば、300である。なお、フレーク状銀コート銅粉の長軸長さLおよび厚みtは、走査型電子顕微鏡(SEM)によるSEM写真を観察することにより測定することができる。 In the present specification, the flake shape means a shape close to a flat plate or a thin rectangular parallelepiped, and specifically means a shape having an aspect ratio (major axis length L / thickness t) of 3 or more. The upper limit of the aspect ratio is 300, for example. The major axis length L and thickness t of the flaky silver-coated copper powder can be measured by observing an SEM photograph with a scanning electron microscope (SEM).
上記フレーク状銀コート銅粉の平均粒子径は、好ましくは5μm〜25μmであり、より好ましくは5μm〜20μmであり、さらに好ましくは7μm〜20μmである。平均粒子径が5μm以上のフレーク状銀コート銅粉を用いれば、はんだによる喰われが防止され、はんだ付け性に優れる導電性ペーストを得ることができる。また、平均粒子径が25μm以下のフレーク状銀コート銅粉を用いれば、スクリーン印刷にてファインライン印刷がしやすい導電性ペーストを得ることができる。なお、平均粒子径とは、レーザー回折散乱法により得られた粒度分布における積算値50%での粒径(一次粒子径)を意味する。 The average particle diameter of the flaky silver-coated copper powder is preferably 5 μm to 25 μm, more preferably 5 μm to 20 μm, and even more preferably 7 μm to 20 μm. If a flaky silver-coated copper powder having an average particle diameter of 5 μm or more is used, it is possible to obtain a conductive paste that is prevented from being eaten by solder and is excellent in solderability. Moreover, if the flaky silver coat copper powder whose average particle diameter is 25 micrometers or less is used, the electrically conductive paste which is easy to carry out fine line printing by screen printing can be obtained. The average particle size means the particle size (primary particle size) at an integrated value of 50% in the particle size distribution obtained by the laser diffraction scattering method.
上記フレーク状銀コート銅粉において、銀コートの重量割合は、銅粒子に対して、好ましくは5重量%〜20重量%であり、より好ましくは7重量%〜18重量%である。このような範囲であれば、低抵抗かつ安価な導電性ペーストを得ることができる。 In the flaky silver-coated copper powder, the weight ratio of the silver coat is preferably 5% by weight to 20% by weight and more preferably 7% by weight to 18% by weight with respect to the copper particles. Within such a range, a low-resistance and inexpensive conductive paste can be obtained.
上記フレーク状銀コート銅粉の含有割合は、フレーク状銀コート銅粉と、上記フェノキシ樹脂と、上記ヘキサメチレンジイソシアネート系ポリイソシアネート化合物およびブロックイソシアネート化合物との合計量100重量部に対して、好ましくは88重量部〜92重量部である。このような範囲であれば、はんだに対する濡れ性に優れる導電性ペーストを得ることができる。 The content ratio of the flaky silver-coated copper powder is preferably 100 parts by weight based on the total amount of the flaky silver-coated copper powder, the phenoxy resin, and the hexamethylene diisocyanate polyisocyanate compound and the blocked isocyanate compound. It is 88 weight part-92 weight part. If it is such a range, the electrically conductive paste which is excellent in the wettability with respect to a solder can be obtained.
上記フレーク状銀コート銅粉は、任意の適切な方法により製造することができる。例えば、球状粒子を任意の適切な粉砕ミルで粉砕して、フレーク状の銅粉を得た後、該銅粉に対して、置換還元法等の方法により銀をコートして、フレーク状銀コート銅粉が得られ得る。 The said flaky silver coat copper powder can be manufactured by arbitrary appropriate methods. For example, spherical particles are pulverized with any appropriate pulverizing mill to obtain flaky copper powder, and then the copper powder is coated with silver by a method such as a substitution reduction method, thereby flaky silver coat Copper powder can be obtained.
C.バインダー成分
(フェノキシ樹脂)
上記フェノキシ樹脂とは、ビスフェノール化合物とエピハロヒドリンとを反応させて得られるエポキシ樹脂である。フェノキシ樹脂は、1分子内にエポキシ基を2個以上含み得る。フェノキシ樹脂としては、分子量(重合度)の大きいものが好ましく用いられる。フェノキシ樹脂の重量平均分子量は、例えば、10000以上であり、好ましくは30000以上であり、より好ましくは35000以上であり、さらに好ましくは35000〜600000である。高分子量のフェノキシ基樹脂を用いれば、耐熱性に優れる導電性ペーストを得ることができる。また、高分子量のエポキシ樹脂は硬化しやすい(硬化温度が低い、硬化時間が短い)傾向にあり、有利である。重量平均分子量は、GPC(溶媒:THF)により測定され得る。
C. Binder component (phenoxy resin)
The phenoxy resin is an epoxy resin obtained by reacting a bisphenol compound with epihalohydrin. The phenoxy resin can contain two or more epoxy groups in one molecule. As the phenoxy resin, those having a large molecular weight (degree of polymerization) are preferably used. The weight average molecular weight of the phenoxy resin is, for example, 10,000 or more, preferably 30000 or more, more preferably 35000 or more, and further preferably 35,000 to 600,000. When a high molecular weight phenoxy group resin is used, a conductive paste having excellent heat resistance can be obtained. High molecular weight epoxy resins tend to be hardened (low curing temperature, short curing time) and are advantageous. The weight average molecular weight can be measured by GPC (solvent: THF).
上記フェノキシ樹脂としては、例えば、ビスフェノール化合物としてビスフェノールAを用いて得られたビスフェノールA型フェノキシ樹脂、ビスフェノールFを用いて得られたビスフェノールF型フェノキシ樹脂等が挙げられる。好ましくは、ビスフェノールA型フェノキシ樹脂が用いられる。ビスフェノールA型フェノキシ樹脂を用いれば、ITO層への密着性を向上させる効果、およびはんだによる喰われを防止する効果が顕著となる。 Examples of the phenoxy resin include a bisphenol A type phenoxy resin obtained using bisphenol A as a bisphenol compound, a bisphenol F type phenoxy resin obtained using bisphenol F, and the like. Preferably, bisphenol A type phenoxy resin is used. If the bisphenol A type phenoxy resin is used, the effect of improving the adhesion to the ITO layer and the effect of preventing the biting by the solder become remarkable.
上記フェノキシ樹脂の含有割合は、フェノキシ樹脂と上記ヘキサメチレンジイソシアネート系ポリイソシアネート化合物およびブロックイソシアネート化合物との合計量に対して、好ましくは40重量%〜65重量%であり、より好ましくは50重量%〜60重量%である。このような範囲であれば、はんだによる喰われが防止され、はんだ付け性に優れる導電性ペーストを得ることができる。 The content of the phenoxy resin is preferably 40% by weight to 65% by weight, more preferably 50% by weight to the total amount of the phenoxy resin, the hexamethylene diisocyanate polyisocyanate compound and the blocked isocyanate compound. 60% by weight. If it is such a range, the biting by a solder is prevented and the electrically conductive paste which is excellent in solderability can be obtained.
(ヘキサメチレンジイソシアネート系ポリイソシアネート化合物)
上記ヘキサメチレンジイソシアネート系ポリイソシアネート化合物としては、ビューレットタイプ、またはイソシアヌレートタイプのヘキサメチレンジイソシアネート系ポリイソシアネート化合物が用いられ得る。好ましくは、イソシアヌレートタイプのヘキサメチレンジイソシアネート系ポリイソシアネート化合物(一般式(1))が用いられる。
(Hexamethylene diisocyanate polyisocyanate compound)
As the hexamethylene diisocyanate polyisocyanate compound, a burette type or isocyanurate type hexamethylene diisocyanate polyisocyanate compound may be used. Preferably, an isocyanurate type hexamethylene diisocyanate polyisocyanate compound (general formula (1)) is used.
上記ヘキサメチレンジイソシアネート系ポリイソシアネート化合物の含有割合は、フェノキシ樹脂とヘキサメチレンジイソシアネート系ポリイソシアネート化合物およびブロックイソシアネート化合物との合計量100重量部に対して、好ましくは35重量部〜60重量部であり、より好ましくは40重量部〜50重量部である。また、上記ヘキサメチレンジイソシアネート系ポリイソシアネート化合物と、上記ブロックイソシアネート化合物とを併用してもよい。この場合、ヘキサメチレンジイソシアネート系ポリイソシアネート化合物および上記ブロックイソシアネート化合物の合計含有割合は、フェノキシ樹脂とヘキサメチレンジイソシアネート系ポリイソシアネート化合物およびブロックイソシアネート化合物との合計量100重量部に対して、好ましくは35重量部〜60重量部であり、より好ましくは40重量部〜50重量部である。 The content ratio of the hexamethylene diisocyanate polyisocyanate compound is preferably 35 parts by weight to 60 parts by weight with respect to 100 parts by weight of the total amount of the phenoxy resin, the hexamethylene diisocyanate polyisocyanate compound and the blocked isocyanate compound, More preferably, it is 40 to 50 parts by weight. Moreover, you may use together the said hexamethylene diisocyanate type polyisocyanate compound and the said block isocyanate compound. In this case, the total content ratio of the hexamethylene diisocyanate-based polyisocyanate compound and the blocked isocyanate compound is preferably 35 wt. Part to 60 parts by weight, and more preferably 40 parts to 50 parts by weight.
(ブロックイソシアネート化合物)
ブロックイソシアネート化合物としては、本発明の効果が得られる限り、任意の適切な化合物が用いられ得る。ブロックイソシアネート化合物は、例えば、イソシアネート化合物のイソシアネート基と、ブロック剤とを反応させて得られ、該イソシアネート基がブロック剤により保護された化合物である。ブロックイソシアネートを用いれば、導電性ペーストのポットライフを向上させ得る。
(Block isocyanate compound)
As the blocked isocyanate compound, any appropriate compound can be used as long as the effects of the present invention are obtained. The blocked isocyanate compound is a compound obtained, for example, by reacting an isocyanate group of an isocyanate compound with a blocking agent, and the isocyanate group is protected by the blocking agent. If block isocyanate is used, the pot life of an electrically conductive paste can be improved.
上記イソシアネート化合物としては、例えば、トリレンジイソシアネート(TDI)、ジフェニルメタンジイソシアネート(MDI)、ヘキサメチレンジイソシアネート(HDI)、イソホロンジイソシアネート(IPDI)等が挙げられる。上記ブロック剤としては、オキシム化合物、ラクタム化合物、フェノール化合物、アルコール化合物、アミン化合物、活性メチレン化合物、ピラゾール化合物、メルカプタン化合物、イミダゾール系化合物、イミド系化合物等を挙げることができる。 Examples of the isocyanate compound include tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), and the like. Examples of the blocking agent include oxime compounds, lactam compounds, phenol compounds, alcohol compounds, amine compounds, active methylene compounds, pyrazole compounds, mercaptan compounds, imidazole compounds, imide compounds, and the like.
上記ブロックイソシアネート化合物の含有割合は、フェノキシ樹脂とヘキサメチレンジイソシアネート系ポリイソシアネート化合物およびブロックイソシアネート化合物との合計量100重量部に対して、好ましくは35重量部〜60重量部であり、より好ましくは40重量部〜50重量部である。 The content ratio of the blocked isocyanate compound is preferably 35 parts by weight to 60 parts by weight, more preferably 40 parts by weight with respect to 100 parts by weight of the total amount of the phenoxy resin, the hexamethylene diisocyanate polyisocyanate compound and the blocked isocyanate compound. Parts by weight to 50 parts by weight.
D.リン含有有機チタネート
上記リン含有有機チタネートとしては、例えば、テトラ(2,2−ジアリルオキシメチル−1−ブチル)ビス(ジ−トリデシル)ホスファイトチタネート、ビス(ジオクチルパイロホスフェート)オキシアセテートチタネート、テトラオクチルビス(ジトリデシルホスファイト)チタネート、テトライソプロピルビス(ジオクチルホスファイト)チタネート、イソプロピルトリス(ジオクチルパイロホスフェート)チタネート、ビス(ジオクチルパイロホスフェート)エチレンチタネート等が挙げられる。好ましくは、ホスフェート基を有するリン含有有機チタネートが用いられ、より好ましくは、ビス(ジオクチルパイロホスフェート)オキシアセテートチタネートが用いられる。
D. Phosphorus-containing organic titanate Examples of the phosphorus-containing organic titanate include tetra (2,2-diallyloxymethyl-1-butyl) bis (di-tridecyl) phosphite titanate, bis (dioctylpyrophosphate) oxyacetate titanate, and tetraoctyl. Examples thereof include bis (ditridecyl phosphite) titanate, tetraisopropyl bis (dioctyl phosphite) titanate, isopropyl tris (dioctyl pyrophosphate) titanate, and bis (dioctyl pyrophosphate) ethylene titanate. Preferably, a phosphorus-containing organic titanate having a phosphate group is used, and more preferably, bis (dioctylpyrophosphate) oxyacetate titanate is used.
上記リン含有有機チタネートの含有割合は、上記フレーク状銀コート銅粉100重量部に対して、好ましくは1重量部〜3重量部であり、より好ましくは1.5重量部〜2.5重量部である。このような範囲であれば、はんだに対する濡れ性に優れる導電性ペーストを得ることができる。 The content ratio of the phosphorus-containing organic titanate is preferably 1 to 3 parts by weight, more preferably 1.5 to 2.5 parts by weight, with respect to 100 parts by weight of the flaky silver-coated copper powder. It is. If it is such a range, the electrically conductive paste which is excellent in the wettability with respect to a solder can be obtained.
E.アルカノールアミン
上記アルカノールアミンは、上記導電性ペースト上ではんだ付けを行う際に、フラックスとしての機能を発揮し得、特に、はんだに対する濡れ性の向上に寄与し得る。また、アルカノールアミンを用いれば、はんだによる喰われが防止されて、はんだ付け性に優れる導電性ペーストを得ることができる。さらには、アルカノールアミンにより、フレーク状銀コート銅粉の表面に保護膜を形成させることができる。
E. Alkanolamine The alkanolamine can exhibit a function as a flux when soldering on the conductive paste, and can particularly contribute to improvement of wettability to solder. In addition, when alkanolamine is used, it is possible to obtain a conductive paste that is prevented from being eroded by solder and is excellent in solderability. Furthermore, a protective film can be formed on the surface of the flaky silver-coated copper powder by alkanolamine.
上記アルカノールアミンは、モノアルカノールアミンであってもよく、ジアルカノールアミンであってもよく、トリアルカノールアミンであってもよい。アルカノールアミンとしては、例えば、モノエタノールアミン、ジエタノールアミン、トリエタノールアミン、モノプロパノールアミン等が挙げられる。なかでも好ましくは、トリエタノールアミンである。トリエタノールアミンを用いれば、はんだに対する濡れ性により優れる導電性ペーストを得ることができる。 The alkanolamine may be a monoalkanolamine, a dialkanolamine, or a trialkanolamine. Examples of the alkanolamine include monoethanolamine, diethanolamine, triethanolamine, monopropanolamine and the like. Of these, triethanolamine is preferable. If triethanolamine is used, a conductive paste that is superior in wettability to solder can be obtained.
上記アルカノールアミンの含有割合は、上記フレーク状銀コート銅粉100重量部に対して、好ましくは1重量部〜3重量部であり、より好ましくは1.5重量部〜2.5重量部である。このような範囲であれば、はんだに対する濡れ性に優れる導電性ペーストを得ることができる。 The content of the alkanolamine is preferably 1 to 3 parts by weight, more preferably 1.5 to 2.5 parts by weight, with respect to 100 parts by weight of the flaky silver-coated copper powder. . If it is such a range, the electrically conductive paste which is excellent in the wettability with respect to a solder can be obtained.
F.その他の添加剤
本発明の導電性ペーストは、任意の適切なその他の添加剤をさらに含み得る。その他の添加剤としては、例えば、消泡剤、酸化防止剤、粘度調整剤、希釈剤、沈降防止材、レベリング剤、カップリング剤等が挙げられる。
F. Other Additives The conductive paste of the present invention may further contain any appropriate other additive. Examples of other additives include antifoaming agents, antioxidants, viscosity modifiers, diluents, anti-settling materials, leveling agents, and coupling agents.
1つの実施形態においては、上記導電性ペーストは、消泡剤をさらに含む。消泡剤としては、例えば、シリコン系消泡剤、アクリル系消泡剤等が挙げられる。消泡剤の添加量は、限定されるものではないが、スクリーン印刷時の消泡に必要な最小量が好ましい。 In one embodiment, the conductive paste further includes an antifoaming agent. Examples of the antifoaming agent include a silicon antifoaming agent and an acrylic antifoaming agent. The addition amount of the antifoaming agent is not limited, but the minimum amount necessary for defoaming during screen printing is preferable.
上記導電性ペーストは、溶剤を含んでいてもよい。該溶剤としては、導電性ペーストに含まれる上記バインダー成分(フェノキシ樹脂、ヘキサメチレンジイソシアネート系ポリイソシアネート化合物、ブロックイソシアネート化合物)を溶解し得る溶剤が好ましく用いられ得る。また、導電性ペーストをスクリーン印刷する際に連続印刷を可能とし得る蒸気圧および沸点を有する溶剤が好ましく用いられ得る。上記溶剤としては、例えば、ブチルカルビトール、エチルカルビトール、γ―ブチロラクトン等の有機溶剤が挙げられる。溶剤は、1種類を単独で使用してもよく、2種類以上を組み合わせて使用してもよい。 The conductive paste may contain a solvent. As the solvent, a solvent capable of dissolving the binder component (phenoxy resin, hexamethylene diisocyanate polyisocyanate compound, block isocyanate compound) contained in the conductive paste can be preferably used. A solvent having a vapor pressure and a boiling point that can enable continuous printing when screen-printing the conductive paste can be preferably used. Examples of the solvent include organic solvents such as butyl carbitol, ethyl carbitol, and γ-butyrolactone. A solvent may be used individually by 1 type and may be used in combination of 2 or more types.
G.導電性ペーストの製造方法
本発明の導電性ペーストは、任意の適切な方法により製造することができる。例えば、フェノキシ樹脂を溶剤で溶解してワニスを調製し、該ワニスに、フレーク状銀コート銅粉、バインダー成分、リン含有有機チタネートおよびアルカノールアミンを添加し、攪拌して得ることができる。各成分は、任意の適切な順序で添加され得る。各成分を攪拌する方法としては、自公転ミキサー、三本ロール、ニーダー等を用いた方法が採用され得る。
G. Manufacturing Method of Conductive Paste The conductive paste of the present invention can be manufactured by any appropriate method. For example, a phenoxy resin can be dissolved in a solvent to prepare a varnish, and flaky silver-coated copper powder, a binder component, a phosphorus-containing organic titanate and an alkanolamine can be added to the varnish and stirred. Each component can be added in any suitable order. As a method of stirring each component, a method using a self-revolving mixer, a triple roll, a kneader or the like can be employed.
代表的には、本発明の導電性ペーストは、透明導電性フィルム上に塗工して用いられ得る。例えば、透明導電性フィルムに形成された透明導電層(例えば、ITO層)上に、導電性ペーストを任意の適切な方法により塗布し、その後、加熱硬化して用いられる。上記塗布方法としては、スクリーン印刷法、フレクシャー印刷法、グラビア印刷法等の印刷法;スプレー法、刷毛塗り、バーコート法等が挙げられる。好ましくは、スクリーン印刷法が用いられる。 Typically, the conductive paste of the present invention can be used by coating on a transparent conductive film. For example, a conductive paste is applied on a transparent conductive layer (for example, ITO layer) formed on a transparent conductive film by any appropriate method, and then heated and cured. Examples of the coating method include screen printing, flexure printing, gravure printing, and the like; spraying, brushing, bar coating, and the like. Preferably, a screen printing method is used.
上記のとおり、本発明の導電性ペーストは、低温で硬化し得る。導電性ペーストの硬化温度は、好ましくは130℃以下であり、より好ましくは120℃以下であり、さらに好ましくは80℃以上100℃未満である。また、加熱硬化の時間は、例えば、10分〜60分である。 As described above, the conductive paste of the present invention can be cured at a low temperature. The curing temperature of the conductive paste is preferably 130 ° C. or lower, more preferably 120 ° C. or lower, and further preferably 80 ° C. or higher and lower than 100 ° C. The time for heat curing is, for example, 10 minutes to 60 minutes.
以下、実施例によって本発明を具体的に説明するが、本発明はこれら実施例によって限定されるものではない。また、実施例において、特に明記しない限り、「部」および「%」は重量基準である。 EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited by these Examples. In Examples, unless otherwise specified, “parts” and “%” are based on weight.
[実施例1]
フェノキシ樹脂(三菱化学社製、商品名「JER1256」、ビスフェノールA型フェノキシ樹脂、重量平均分子量:50000)6.7重量部と、ヘキサメチレンジイソシアネート系ポリイソシアネート化合物(イソシアヌレートタイプ、NCO%:23.1重量%)4.4重量部と、ブチルカルビトールとを混合してワニスを調製した。
上記ワニス(固形分:11.1重量部)に、フレーク状銀コート銅粉(平均粒子径:8μm〜10μm、銀コート量:15重量%、アスペクト比:45)100重量部と、トリエタノールアミン1重量部と、リン含有有機チタネート(ビス(ジオクチルパイロホスフェート)オキシアセテートチタネート)1重量部と消泡剤とを加えて、導電性ペーストを得た。
[Example 1]
6.7 parts by weight of a phenoxy resin (Mitsubishi Chemical Co., Ltd., trade name “JER1256”, bisphenol A type phenoxy resin, weight average molecular weight: 50000), hexamethylene diisocyanate polyisocyanate compound (isocyanurate type, NCO%: 23. 1 wt%) 4.4 parts by weight and butyl carbitol were mixed to prepare a varnish.
To the varnish (solid content: 11.1 parts by weight), flaky silver-coated copper powder (average particle size: 8 μm to 10 μm, silver coating amount: 15% by weight, aspect ratio: 45), and triethanolamine 1 part by weight, 1 part by weight of phosphorus-containing organic titanate (bis (dioctylpyrophosphate) oxyacetate titanate) and an antifoaming agent were added to obtain a conductive paste.
[実施例2]
トリエタノールアミンの配合量を1.5重量部とし、リン含有有機チタネート(ビス(ジオクチルパイロホスフェート)オキシアセテートチタネート)の配合量を1.5重量部としたこと以外は、実施例1と同様にして導電性ペーストを得た。
[Example 2]
The same as in Example 1 except that the amount of triethanolamine was 1.5 parts by weight and the amount of phosphorus-containing organic titanate (bis (dioctylpyrophosphate) oxyacetate titanate) was 1.5 parts by weight. As a result, a conductive paste was obtained.
[実施例3]
トリエタノールアミンの配合量を2重量部とし、リン含有有機チタネート(ビス(ジオクチルパイロホスフェート)オキシアセテートチタネート)の配合量を2重量部としたこと以外は、実施例1と同様にして導電性ペーストを得た。
[Example 3]
Conductive paste in the same manner as in Example 1, except that the amount of triethanolamine was 2 parts by weight and the amount of phosphorus-containing organic titanate (bis (dioctylpyrophosphate) oxyacetate titanate) was 2 parts by weight. Got.
[実施例4]
トリエタノールアミンの配合量を2.5重量部とし、リン含有有機チタネート(ビス(ジオクチルパイロホスフェート)オキシアセテートチタネート)の配合量を2.5重量部としたこと以外は、実施例1と同様にして導電性ペーストを得た。
[Example 4]
The same as in Example 1 except that the amount of triethanolamine was 2.5 parts by weight and the amount of phosphorus-containing organic titanate (bis (dioctylpyrophosphate) oxyacetate titanate) was 2.5 parts by weight. As a result, a conductive paste was obtained.
[実施例5]
トリエタノールアミンの配合量を3重量部とし、リン含有有機チタネート(ビス(ジオクチルパイロホスフェート)オキシアセテートチタネート)の配合量を3重量部としたこと以外は、実施例1と同様にして導電性ペーストを得た。
[Example 5]
Conductive paste in the same manner as in Example 1 except that the amount of triethanolamine was 3 parts by weight and the amount of phosphorus-containing organic titanate (bis (dioctylpyrophosphate) oxyacetate titanate) was 3 parts by weight. Got.
[実施例6]
フェノキシ樹脂(三菱化学社製、商品名「JER1256」、ビスフェノールA型フェノキシ樹脂、重量平均分子量:50000)7.2重量部と、ヘキサメチレンジイソシアネート系ポリイソシアネート化合物(イソシアヌレートタイプ、NCO%:23.1重量%)3.9重量部と、ブチルカルビトールとを混合してワニスを調製した。
上記ワニス(固形分:11.1重量部)に、フレーク状銀コート銅粉(平均粒子径:8μm〜10μm、銀コート量:15重量%、アスペクト比:45)100重量部と、トリエタノールアミン2.5重量部と、リン含有有機チタネート(ビス(ジオクチルパイロホスフェート)オキシアセテートチタネート)2.5重量部と消泡剤とを加えて、導電性ペーストを得た。
[Example 6]
7.2 parts by weight of a phenoxy resin (manufactured by Mitsubishi Chemical Corporation, trade name “JER1256”, bisphenol A type phenoxy resin, weight average molecular weight: 50000) and a hexamethylene diisocyanate polyisocyanate compound (isocyanurate type, NCO%: 23. 1 wt%) 3.9 parts by weight and butyl carbitol were mixed to prepare a varnish.
To the varnish (solid content: 11.1 parts by weight), flaky silver-coated copper powder (average particle size: 8 μm to 10 μm, silver coating amount: 15% by weight, aspect ratio: 45), and triethanolamine 2.5 parts by weight, 2.5 parts by weight of phosphorus-containing organic titanate (bis (dioctylpyrophosphate) oxyacetate titanate) and an antifoaming agent were added to obtain a conductive paste.
[実施例7]
フェノキシ樹脂(三菱化学社製、商品名「JER1256」、ビスフェノールA型フェノキシ樹脂、重量平均分子量:50000)の配合量を6.7重量部とし、ヘキサメチレンジイソシアネート系ポリイソシアネート化合物(イソシアヌレートタイプ、NCO%:23.1重量%)の配合量を4.4重量部としたこと以外は、実施例6と同様にして、導電性ペーストを得た。
[Example 7]
The blending amount of phenoxy resin (Mitsubishi Chemical Corporation, trade name “JER1256”, bisphenol A type phenoxy resin, weight average molecular weight: 50000) is 6.7 parts by weight, hexamethylene diisocyanate polyisocyanate compound (isocyanurate type, NCO) %: 23.1% by weight) was obtained in the same manner as in Example 6 except that the blending amount was 4.4 parts by weight.
[実施例8]
フェノキシ樹脂(三菱化学社製、商品名「JER1256」、ビスフェノールA型フェノキシ樹脂、重量平均分子量:50000)の配合量を6.1重量部とし、ヘキサメチレンジイソシアネート系ポリイソシアネート化合物(イソシアヌレートタイプ、NCO%:23.1重量%)の配合量を5.0重量部としたこと以外は、実施例6と同様にして、導電性ペーストを得た。
[Example 8]
The blending amount of phenoxy resin (Mitsubishi Chemical Corporation, trade name “JER1256”, bisphenol A type phenoxy resin, weight average molecular weight: 50000) is 6.1 parts by weight, hexamethylene diisocyanate polyisocyanate compound (isocyanurate type, NCO). %: 23.1% by weight) was obtained in the same manner as in Example 6 except that the blending amount was 5.0 parts by weight.
[実施例9]
フェノキシ樹脂(三菱化学社製、商品名「JER1256」、ビスフェノールA型フェノキシ樹脂、重量平均分子量:50000)6.6重量部と、ヘキサメチレンジイソシアネート系ポリイソシアネート化合物(イソシアヌレートタイプ、NCO%:23.1重量%)4.9重量部と、ブチルカルビトールとを混合してワニスを調製した。
上記ワニス(固形分:11.5重量部)に、フレーク状銀コート銅粉(平均粒子径:8μm〜10μm、銀コート量:15重量%、アスペクト比:45)100重量部と、トリエタノールアミン2.5重量部と、リン含有有機チタネート(ビス(ジオクチルパイロホスフェート)オキシアセテートチタネート)2.5重量部とを加えて、導電性ペーストを得た。
[Example 9]
6.6 parts by weight of a phenoxy resin (Mitsubishi Chemical Co., Ltd., trade name “JER1256”, bisphenol A type phenoxy resin, weight average molecular weight: 50000), hexamethylene diisocyanate polyisocyanate compound (isocyanurate type, NCO%: 23. 1 wt.%) 4.9 parts by weight and butyl carbitol were mixed to prepare a varnish.
To the varnish (solid content: 11.5 parts by weight), flaky silver-coated copper powder (average particle size: 8 μm to 10 μm, silver coating amount: 15% by weight, aspect ratio: 45), 100 parts by weight, and triethanolamine 2.5 parts by weight and 2.5 parts by weight of phosphorus-containing organic titanate (bis (dioctylpyrophosphate) oxyacetate titanate) were added to obtain a conductive paste.
[実施例10]
ヘキサメチレンジイソシアネート系ポリイソシアネート化合物(イソシアヌレートタイプ、NCO%:23.1重量%)4.9重量部に代えて、ブロックイソシアネート化合物(旭化成ケミカルズ社製、商品名「デュラネート SBN−70D」)4.9重量部を用いたこと以外は、実施例9と同様にして導電性ペーストを得た。
[Example 10]
3. Hexamethylene diisocyanate-based polyisocyanate compound (isocyanurate type, NCO%: 23.1 wt%) Instead of 4.9 parts by weight, blocked isocyanate compound (product name "Duranate SBN-70D" manufactured by Asahi Kasei Chemicals) A conductive paste was obtained in the same manner as in Example 9 except that 9 parts by weight were used.
[実施例11]
フレーク状銀コート銅粉(平均粒子径:8μm〜10μm、銀コート量:15重量%、アスペクト比:45)100重量部に代えて、フレーク状銀コート銅粉(平均粒子径:5μm〜7μm、銀コート量:5重量%、アスペクト比:30)100重量部を用いたこと以外は、実施例9と同様にして導電性ペーストを得た。
[Example 11]
Instead of 100 parts by weight of flaky silver-coated copper powder (average particle diameter: 8 μm to 10 μm, silver coating amount: 15 wt%, aspect ratio: 45), flaky silver coated copper powder (average particle diameter: 5 μm to 7 μm, A conductive paste was obtained in the same manner as in Example 9 except that 100 parts by weight of silver coating amount: 5% by weight, aspect ratio: 30) was used.
[比較例1]
トリエタノールアミンおよびリン含有有機チタネートを添加しなかったこと以外は、実施例1と同様にして、導電性ペーストを得た。
[Comparative Example 1]
A conductive paste was obtained in the same manner as in Example 1 except that triethanolamine and phosphorus-containing organic titanate were not added.
[比較例2]
フェノキシ樹脂(三菱化学社製、商品名「JER1256」、ビスフェノールA型フェノキシ樹脂、重量平均分子量:50000)の配合量を8.2重量部とし、ヘキサメチレンジイソシアネート系ポリイソシアネート化合物(イソシアヌレートタイプ、NCO%:23.1重量%)の配合量を5.5重量部としたこと以外は、比較例1と同様にして、導電性ペーストを得た。
[Comparative Example 2]
The blending amount of phenoxy resin (Mitsubishi Chemical Corporation, trade name “JER1256”, bisphenol A type phenoxy resin, weight average molecular weight: 50000) is 8.2 parts by weight, hexamethylene diisocyanate polyisocyanate compound (isocyanurate type, NCO). %: 23.1% by weight) was obtained in the same manner as in Comparative Example 1 except that the blending amount was 5.5 parts by weight.
[比較例3]
フレーク状銀コート銅粉100重量部に代えて、球状銀コート銅粉(平均粒子径:6μm〜10μm、銀コート量:10重量%)100重量部を用いたこと以外は、実施例9と同様にして、導電性ペーストを得た。
[Comparative Example 3]
The same as Example 9 except that 100 parts by weight of spherical silver-coated copper powder (average particle diameter: 6 μm to 10 μm, silver coat amount: 10% by weight) was used instead of 100 parts by weight of flaky silver-coated copper powder. Thus, a conductive paste was obtained.
[比較例4]
フレーク状銀コート銅粉100重量部に代えて、フレーク状銀粉(平均粒子径:7μm〜15μm、アスペクト比:55)100重量部を用いたこと以外は、実施例9と同様にして、導電性ペーストを得た。
[Comparative Example 4]
In place of 100 parts by weight of the flaky silver-coated copper powder, the same as in Example 9 except that 100 parts by weight of flaky silver powder (average particle diameter: 7 μm to 15 μm, aspect ratio: 55) was used. A paste was obtained.
[比較例5]
フレーク状銀コート銅粉100重量部に代えて、フレーク状銅粉(平均粒子径:8μm〜10μm、アスペクト比:45)100重量部を用いたこと以外は、実施例9と同様にして、導電性ペーストを得た。
[Comparative Example 5]
Instead of 100 parts by weight of flaky silver-coated copper powder, conductive material was obtained in the same manner as in Example 9 except that 100 parts by weight of flaky copper powder (average particle diameter: 8 μm to 10 μm, aspect ratio: 45) was used. Sex paste was obtained.
[比較例6]
フェノキシ樹脂(三菱化学社製、商品名「JER1256」、ビスフェノールA型フェノキシ樹脂、重量平均分子量:50000)4.9重量部と、ヘキサメチレンジイソシアネート系ポリイソシアネート化合物(イソシアヌレートタイプ、NCO%:23.1重量%)3.2重量部と、ブチルカルビトールとを混合してワニスを調製した。
上記ワニス(固形分:8.1重量部)に、フレーク状銀コート銅粉(平均粒子径:8μm〜10μm、銀コート量:15重量%、アスペクト比:45)100重量部と、トリエタノールアミン2.5重量部と、リン含有有機チタネート(ビス(ジオクチルパイロホスフェート)オキシアセテートチタネート)2.5重量部と消泡剤とを加えて、導電性ペーストを得た。
[Comparative Example 6]
4.9 parts by weight of a phenoxy resin (Mitsubishi Chemical Co., Ltd., trade name “JER1256”, bisphenol A type phenoxy resin, weight average molecular weight: 50000) and a hexamethylene diisocyanate polyisocyanate compound (isocyanurate type, NCO%: 23. 1 wt%) 3.2 parts by weight and butyl carbitol were mixed to prepare a varnish.
To the varnish (solid content: 8.1 parts by weight), flaky silver-coated copper powder (average particle diameter: 8 μm to 10 μm, silver coating amount: 15% by weight, aspect ratio: 45) and 100 parts by weight of triethanolamine 2.5 parts by weight, 2.5 parts by weight of phosphorus-containing organic titanate (bis (dioctylpyrophosphate) oxyacetate titanate) and an antifoaming agent were added to obtain a conductive paste.
[比較例7]
フェノール樹脂(群栄化学工業社製、商品名「レジトップPL4348」)11.5重量部と、ブチルカルビトールとを混合してワニスを調製した。このワニスを用いたこと以外は、実施例9と同様にして、導電性ペーストを得た。
[Comparative Example 7]
A varnish was prepared by mixing 11.5 parts by weight of a phenolic resin (manufactured by Gunei Chemical Industry Co., Ltd., trade name “Resitop PL4348”) and butyl carbitol. A conductive paste was obtained in the same manner as in Example 9 except that this varnish was used.
<評価>
実施例および比較例で得られた導電性ペーストを以下の評価に供した。結果を表1に示す。
<Evaluation>
The conductive pastes obtained in the examples and comparative examples were subjected to the following evaluation. The results are shown in Table 1.
(1)体積抵抗率
ガラスエポキシ基板上に形成させた2つの銅電極の間で、導電性ペーストをライン状に印刷し、その後、エアーオーブンを用いて加熱して(実施例1〜11および比較例1〜6:120℃で30分間、比較例7:160℃で30分間)、導電性ペーストを硬化させて測定用サンプルを得た。
印刷はスクリーン印刷を採用し、乳剤厚30μmの180メッシュテトロンスクリーンを使用した。ラインは、幅1mm、長さ70mmのサイズとし、10本形成させた。
電極間の抵抗値を4端子法により測定した。得られた抵抗値から以下の式により、体積抵抗を求めた。なお、塗膜厚さ(D)は10本のラインの厚さの平均値であり、測定抵抗値(R)は、10本のラインの測定抵抗値の平均値である。
体積抵抗率σ=W×D×R/L
σ:体積抵抗率(Ω・cm)
W:塗膜幅 (cm)
D:塗膜厚さ (cm)(10本のラインの塗膜厚さの平均値)
L:塗膜長 (cm)
R:測定抵抗値(Ω) (10本のラインの測定抵抗値の平均値)
(1) Volume resistivity Between two copper electrodes formed on a glass epoxy substrate, a conductive paste was printed in a line shape, and then heated using an air oven (Examples 1 to 11 and comparison) Examples 1 to 6: 120 ° C. for 30 minutes, Comparative Example 7: 160 ° C. for 30 minutes), the conductive paste was cured to obtain a measurement sample.
The printing employed screen printing, and a 180 mesh Tetron screen with an emulsion thickness of 30 μm was used. Ten lines were formed with a width of 1 mm and a length of 70 mm.
The resistance value between the electrodes was measured by a four-terminal method. From the obtained resistance value, the volume resistance was determined by the following formula. The coating thickness (D) is an average value of the thicknesses of 10 lines, and the measured resistance value (R) is an average value of the measured resistance values of 10 lines.
Volume resistivity σ = W × D × R / L
σ: Volume resistivity (Ω · cm)
W: Coating width (cm)
D: Coating thickness (cm) (average value of coating thickness of 10 lines)
L: Coating film length (cm)
R: measured resistance value (Ω) (average value of measured resistance values of 10 lines)
(2)アセトンラビング試験
上記(1)と同様に測定サンプルを得た。アセトンをしみ込ませたペーパータオルを、ライン状の導電ペースト上で5往復させ、該ペーストが拭き取られるか否かを確認し、以下の基準で評価した。
○:全くペーストが拭き取られない。
△:ペーストが少し拭き取られる。
×:ペーストが完全に拭き取られる。
(2) Acetone rubbing test A measurement sample was obtained in the same manner as in (1) above. A paper towel soaked with acetone was reciprocated five times on the line-shaped conductive paste to confirm whether or not the paste was wiped off, and evaluated according to the following criteria.
○: The paste is not wiped off at all.
Δ: The paste is wiped off a little.
X: The paste is completely wiped off.
(3)はんだ付け性試験
片面銅張りガラスエポキシ基板に、導電性ペーストを乳剤厚30μmの180メッシュテトロンスクリーンを使用して、15×20mmの面積で印刷する。このスクリーン印刷後、エアーオーブンで加熱硬化した後(実施例1〜11および比較例1〜6:120℃で30分間、比較例7:160℃で30分間)、室温まで冷却し、これをサンプルとする。このサンプルを265±5℃に加熱した63Sn/37Pbのはんだに3秒間浸漬し取り出した後、15×20mmのペーストへのはんだ濡れ性を評価した。
○:はんだ濡れ面積80%以上
△:はんだ濡れ面積50%以上、80%未満
△〜×:はんだ濡れ面積20%以上、50%未満
×:はんだ濡れ面積20%未満
(3) Solderability test A conductive paste is printed on a single-sided copper-clad glass epoxy substrate with an area of 15 × 20 mm using a 180 mesh Tetron screen with an emulsion thickness of 30 μm. After this screen printing, after heat-curing in an air oven (Examples 1 to 11 and Comparative Examples 1 to 6: 120 ° C. for 30 minutes, Comparative Example 7: 160 ° C. for 30 minutes), it was cooled to room temperature, and this was sampled And This sample was immersed in a 63Sn / 37Pb solder heated to 265 ± 5 ° C. for 3 seconds and then taken out, and then the solder wettability to a 15 × 20 mm paste was evaluated.
○: Solder wetting area 80% or more △: Solder wetting area 50% or more, less than 80% △ -X: Solder wetting area 20% or more, less than 50% X: Solder wetting area less than 20%
(4)ITOに対する密着性
ITO基板上に導電性ペーストを塗布し、その後、加熱して(実施例1〜11および比較例1〜6:120℃で30分間、比較例7:160℃で30分間)、塗布層を硬化させて、評価サンプルを作製した。
上記評価サンプルを用い、導電性ペーストとITOとの密着性を、JIS K 5600の碁盤目剥離試験により評価した。具体的には、導電性ペースト表面上10mm角中に1mm間隔にカッターで切れ目を入れ、100個の碁盤目を作り、粘着テープをその上に貼り付けた後、剥離し、ITO基板から剥離した碁盤目の数を測定し、以下の基準で密着性を評価した。
〇:剥離した碁盤目の数が1個未満
△:剥離した碁盤目の数が1個以上99個未満
×:剥離した碁盤目の数が99個以上
(4) Adhesiveness to ITO A conductive paste is applied on an ITO substrate and then heated (Examples 1 to 11 and Comparative Examples 1 to 6: 30 minutes at 120 ° C., Comparative Example 7: 30 at 160 ° C. Minutes), the coating layer was cured to produce an evaluation sample.
Using the evaluation sample, the adhesion between the conductive paste and ITO was evaluated by a cross-cut peel test of JIS K 5600. Specifically, the surface of the conductive paste is cut into 10 mm squares at intervals of 1 mm with a cutter, 100 grids are made, and an adhesive tape is affixed thereon, then peeled off and peeled off from the ITO substrate. The number of grids was measured and the adhesion was evaluated according to the following criteria.
◯: The number of peeled grids is less than 1 Δ: The number of peeled grids is 1 or more and less than 99 ×: The number of peeled grids is 99 or more
実施例から明らかなように、本発明によれば、低温で硬化し得、かつ、はんだ付け性に優れる導電性ペーストを提供することができる。また、上記アセトンラビング試験の結果から、本発明の導電性ペーストは、十分に硬化していることがわかる。このような導電性ペーストは、はんだによる喰われが防止され得る。さらに、実施例で得られた導電性ペーストは、ITO層との密着性に優れていた。 As is clear from the examples, according to the present invention, it is possible to provide a conductive paste that can be cured at a low temperature and has excellent solderability. Moreover, it can be seen from the results of the acetone rubbing test that the conductive paste of the present invention is sufficiently cured. Such a conductive paste can be prevented from being eroded by solder. Furthermore, the conductive paste obtained in the examples was excellent in adhesion with the ITO layer.
Claims (6)
フェノキシ樹脂と、
ヘキサメチレンジイソシアネート系ポリイソシアネート化合物および/またはブロックイソシアネート化合物と、
リン含有有機チタネートと、
アルカノールアミンとを含み、
該フレーク状銀コート銅粉の含有割合が、該フレーク状銀コート銅粉と、前記フェノキシ樹脂と、前記ヘキサメチレンジイソシアネート系ポリイソシアネート化合物およびブロックイソシアネート化合物との合計量100重量部に対して、88重量部〜92重量部である、
導電性ペースト。 Flaky silver coated copper powder,
Phenoxy resin,
A hexamethylene diisocyanate polyisocyanate compound and / or a blocked isocyanate compound;
A phosphorus-containing organic titanate;
Alkanolamine and
The content of the flaky silver-coated copper powder is 88 parts by weight based on a total amount of 100 parts by weight of the flaky silver-coated copper powder, the phenoxy resin, the hexamethylene diisocyanate polyisocyanate compound, and the blocked isocyanate compound. Parts by weight to 92 parts by weight,
Conductive paste.
該銀コートの重量割合が、該銅粒子に対して、5重量%〜20重量%である、請求項1または2に記載の導電性ペースト。 The flaky silver-coated copper powder is composed of core copper particles and a silver coat that coats the copper particles,
The electrically conductive paste of Claim 1 or 2 whose weight ratio of this silver coat is 5 to 20 weight% with respect to this copper particle.
The conductive paste according to any one of claims 1 to 5, wherein a content ratio of the alkanolamine is 1 part by weight to 3 parts by weight with respect to 100 parts by weight of the flaky silver-coated copper powder.
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PCT/JP2016/066475 WO2016199678A1 (en) | 2015-06-09 | 2016-06-02 | Conductive paste |
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JP6567921B2 (en) * | 2014-08-29 | 2019-08-28 | Dowaエレクトロニクス株式会社 | Silver-coated copper powder and method for producing the same |
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- 2016-05-23 TW TW105115959A patent/TWI657117B/en active
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CN110809806A (en) * | 2017-07-03 | 2020-02-18 | 同和电子科技有限公司 | Conductive paste |
CN110809806B (en) * | 2017-07-03 | 2021-07-06 | 同和电子科技有限公司 | Conductive paste |
WO2023189945A1 (en) * | 2022-03-29 | 2023-10-05 | バンドー化学株式会社 | Electroconductive ink |
JP7373096B1 (en) * | 2022-03-29 | 2023-11-01 | バンドー化学株式会社 | conductive ink |
Also Published As
Publication number | Publication date |
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HK1247437B (en) | 2020-03-20 |
TW201708431A (en) | 2017-03-01 |
TWI657117B (en) | 2019-04-21 |
CN107615402B (en) | 2019-05-31 |
WO2016199678A1 (en) | 2016-12-15 |
JP6151742B2 (en) | 2017-06-21 |
CN107615402A (en) | 2018-01-19 |
US20180163069A1 (en) | 2018-06-14 |
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